Method of removing foul smelling and sulphur compounds



Patented May 23, 1933 u TEo STATES PSATEVNT oFF1c JULES H. mar, or EL rnso, TEXAS; HARRIET rl ia nr, nxnournixor sAI n JULES H. 'nin'r, DECEASED, ASSIGNIOR T L. J. iirar, or NEW YORK, N. Y.

, maybe made up as follows:

METHOD or tiiiviovine FOUL SMEIJTJING'AND1 SULPHUR GOMPOUNDS No Drawing. Original application filed March 23,1929, Serial No. 349,520. Divided and this application filed January 20, 1930. Serial No. 422,224. I

My invention relates to the method otre moving the foul smellingand sulphur compounds. from volatile and other petroleum base liquids. Practicallyall distilled petroleum base liquids require purification and removal of these substances. Just what form the sulphur compounds are in, in petroleumv liquids, is extremely uncertain and subject to much discussion at the present time. After many tests, I have discoveredthat a new porous, active,-chemical compound can be readily made thathas many desirable.

Many tests have proven that my composition will remove sulphur compounds from petroa leum liquids when other treatments have failed.

The composition, in the preferred form regular chemical A suitable iron boat pan set over a low brick fire-place is charged with 16 O parts by weight of water in which 18 dlSSOlVGCl 100 parts of caustic soda and then parts of powdered litharge. To the hot liquid, 200 parts of small lump caustic lime is added and the mass raked over until it becomes a dry, clinker-like porousproduct, the 495 parts by weight of thecharge yielding 400 parts of'the product. The dust dry mass still contains parts of water practically all in the strong chemical combination.

The resulting product is light yellow in color, of a hydroscopic nature, slightly more than calcium carbide, yet easily kept in air tight iron containers. Exposure to sunlight for a year did not change the chemical activity of the product when kept inan air tight glassjar. V

When the composition is ground in a hand porcelain mortar with elemental powdered sulphur, they will start to combine at once,

as evidenced by the mikture changing color and eventually becoming black, due to the formation of lead sulphide. v

-"The porous chemical composition is easily ground in a coffee mill type of grinder.

The composition can be used in a-coarse condition for percolation upwards or downwards through it; or the screened out fines can be used in the agitating contact method of treatment.

The composition is particularly advantageous for purifying volatile petroleum base solvents due'tothe simple method of percolating .thesolvent upwards or downwards through the porous dry chemical masscontained inaclosed tank under sufficient pres--v sure to cause a flow. V i V V Colloidal suspended matter is usually re moved by percolation through dry clay after the dry chemical treatment in closed vessels, thereby avoiding evaporation losses. 7

The chemicals-in the composition probabl allexist as hydrates inan extremelyactive condition. If the chemical compound. is strongly heated, it becomes brown in color, and when a sample of this mass is ground up with powdered sulphur in a porcelain mortar it does not react-and change color showing that no chemical combination has taken place and that the heated composition is inactive.

Boiling the composition in a sulphur bear-= ing petroleum liquid does notremove the sulphur, whereas, it will remove it in cold contact or cold percolation with the petroleum liquid. I .The boiling probably dehydrates the chemical compound in the petroleum liquid and makes it inactive towards sulphur compounds in solvents oroils. 7

Numerous experiments have been made replacing all or part of the different chemicals used in the general formula. Different alkali and alkali earth-caustics were substituted Different oxides were substituted for the litharge or simple lead, oxide. I The re-' placement of caustic lime with'caustic magnesia is the second best composition and while not as active chemically towards powdered sulphur as the straight caustic lime formula, itlias certain advantages on some petroleum liquids of greater color removal gasoline and powdered sulphur.

In these tests, the powdered material as finished, was tested on sour gasoline to determine its sulphur compound removal property. Starting with the hot caustic soda solution, Zinc oxide was added and after boilingfor a time, caustic lime was added to make the clinker a porous mass. This product was then powdered and tested on In none of these testsdid the compound haveto the same extent, the active quality that the straight caustic soda-lithargecaustic lime compound hada In the next series of tests one-half of the caustic soda wasreplaced with caustic potash, and all the resultant compositions were slow in chemical reaction towards sour gasoline. The caustic soda-potash-lithargelime in this series of tests was also less active than the compoundwithout the-caustic potash.

\Vhere the caustic'soda was replaced e11- tirely by caustic-potash all the different metallic oxide compounds were very slow in action towards sour .gasoline,'and elemental sulphur.

Thesetests covering many combinations showed that the caustic soda-litharge-lime compound was the most active towards sour The next tests were made to determine what the effect would be by the removal of the. lime and substituting magnesia in place of the lime, using the caustic soda litharge combination.

If all the lime is replaced by caustic magnesia (dead burnt magnesia is inert) there is produced the composition, caustic sodalitharge-caustic magnesia, a product-that is not asactive as the straight caustic sodalitharge-caustic lime composition, yet it is practical to use it and though somewhat slower ,in action, its color removal property towards certain petroleum liquids is much greater than where lime is, present. It is known that lime compounds on certain petroleum liquids have a: tendency to produce a'high color towards the red scale.

. Instead "of' the caustic lime, practically 7 pure lime withdifierent percentages of magnesia including dolomite lime, which is about one-half calcium oxide and one-half magnesium oxide, were substituted. Caustic lime with small percentagesqof magnesium oxide gives a compound which is practically elemental sulphur.

equal in chemical action to the straight caustic soda-litharge-caustic lime compound.

Numerous tests show that the caustic sodalitharge-caustic magnesia compound is not as active as the'caustic soda-litharge-caustic lime compound. It is, however, practical to use it in certain cases, where there is a tendency to increase thecolor by the use of the limecompound as compared to the magnesia compound."

In general, repeated tests show that the caustic soda-litharge-caustic lime compound is the most active towards sour gasoline and The caustic soda-litharge-caustic magnesia compound is the second best. All the others will also react but much more slowly with petroleum liquids containing objectionable sulphur compounds or powdered sulphur.- V

' The above different combinations of a caustic alkali, with the different metallic oxides and different ratios of alkali-earth compounds were made and tested, as being the most practical for economic reasons. The chemical compounds, caustic soda-litharge-caustic lime and caustic soda-litharge-caustic magnesia are stable and domot'change or deteriorate after a years time it kept in an air tight iron container. U

In either the caustic sodaslitharge-caustic lime or the caustic soda-litharge-caustic magnesia compound, it is evident that the working ratio of water l-caustic soda 100-- litharge 35-caustic lime or caustic magnesia 200 parts by weight can be varied a great deal and still get a finalproduct which is active towards sour gasoline and elemental sulphur. "However, the ratios as given are what was found most satisfactory and practical in'making up 400 pound batcheswith a one man hand equipment and yielded a product with the greatest chemical activity and porous texture, a very desirable property for economic reasons. Y r

It willbe noted that the ingredients of my composition will not react together with out the presence of water.

This application isadivision of my application Ser. No. 349,520, filed March 23, 1929, which has matured into Patent No. 1,809,554 granted June 9, 193 1. i

I claim: v

1. The method of removing foul smellin and sulphur compounds from volatile an other petroleum base liquids comprising treating the said liquids with the dry hydrous reaction product of a caustic soda solution, litharge and caustic lime at a temperature below that which will dehydrate the said product and render it inactive.

2. The method of removing foul smelling and sulphur compounds from volatile and other petroleum base liquids comprising treating the said liquids with the dry hydrous reaction product of a causticsoda solution, litharge and a compound selected from the group consisting of caustic lime, caustic magnesia at a temperature below that which will dehydrate the said product and render it inactive.

3. The method which comprises treating volatile and other petroleum base liquids with a dry hydrous reaction product of a caustic alkali solution, a metallic oxide and an alkaline earth caustic compound, that has the property of removing foul smelling and sulphur compounds from said liquids and maintaining a temperature for the treatment that is below that which will dehydrate the said product and render it inactive.

In testimony whereof I afiix my signature.

JULES H. HIRT. 

